CA3101704A1

CA3101704A1 - Apparatus and method for measuring water content profiles, interfacial levels, thicknesses and tensions of multiphase dispersions

Info

Publication number: CA3101704A1
Application number: CA3101704A
Authority: CA
Inventors: Guoxing Gu
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-02-06
Filing date: 2020-12-05
Publication date: 2021-08-06
Also published as: US20210255079A1; US11733140B2

Abstract

A apparatus and method for simultaneously measuring water content profiles, surface/interfacial levels, thicknesses and tensions of multiphase dispersions, such as dispersions with water dispersed in produced oils, crude oils, various fuels, distillates, lubricants, paints and polymers, or reversed dispersions with these organic components dispersed in water. The apparatus with 1-16 channels, namely multi-channel scanning water analyzer (MCSWA) and/or tensiometer, comprising a motorized precision vertical stage with multiple capacitive sensors, a heating system with multiple heating cells for keeping the respective sample bottles, and a data acquisition system, where the capacitive sensors can be precisely controlled via a computer to dip into the samples at a preset scanning velocity and the capacitances of the sensors are continuously measured by the data acquisition system. The measured sensor capacitances are used to derive water content profiles, surface/interfacial levels, interfacial thicknesses and surface/interfacial tensions of the respective samples. The apparatus is a good tool for R&D scientists to select chemicals efficiently and can provide reliable data for engineering design and product quality assurance.

Description

Apparatus and Method for Measuring Water Content Profiles, Interfacial levels, Thicknesses and Tensions of Multiphase Dispersions Inventor: Guoxing Gu (Edmonton, CA) Field of the Invention [0001] This specification includes materials in common with a provisional patent application 62/970,710 filed on February 6, 2020 with the same inventor as this application. This application includes some additional information in relation to a method for measuring surface/interfacial tensions using the same apparatus that was developed for measuring water content profiles, surface/interfacial levels and thicknesses of multiphase dispersions, such as dispersions with water dispersed in produced oils, crude oils, various fuels, distillates, lubricants, paints and polymers or reversed dispersions with these organic components dispersed in water, broadening applications of the apparatus.
Background

[0002] A produced oil is a mixture of water, oil and solids in any oil production facilities. The produced oil is commonly stabilized by natural surface active agents and requires intensive chemical and physical treatments to separate water and solids from oil. Knowing water distribution, phase boundaries and interfacial thicknesses in any process vessel are crucial to both operation engineers and R&D scientists as well as management personnel's. Water and basic sediment (BS&W) content in oil must be well controlled to be less than 0.5% for acceptance of downstream pipeline transportation. Enhanced oil recovery technologies are extensively used everywhere, Date recue/ Date received 2020-12-05 they heavily rely on chemical addition to improve oil recovery, but added chemicals adversely impact treatment of produced oils. The added chemicals help oil to liberate from surface of oil sands and then form a dispersion either in the form of oil-in-water (0/W) or water-in-oil (W/0) emulsion. The emulsified dispersions must be treated for oil products. Currently, the water distribution analysis and phase boundary identification are carried out in lab first followed by field confirmation.
Phase boundary visual identification is very difficult for heavy oils due to their dark, viscous and sticky nature. This lab-intensive work is a must in both engineering and operation stages to figure out the best types of chemicals, dosages, chemical working temperature and adding procedure as well as chemical adding location in a line of production and separation vessels, e.g. well heads, well lines, gas and free water knock out vessels, oil/water separation vessels and oil purification vessels.
Water analysis is also important in quality assurance in various downstream oil products (such as fuels and lubricants) and other industry's products (such as paints and polymers). Phase boundaries or interfacial levels can be used to evaluate how much clean oil, emulsion, rag layer and aqueous phases available in a process vessel. Interfacial thicknesses provide additional information for evaluating effectiveness of added chemicals.

[0003] To do water analysis in a lab, firstly, oil samples are taken in bulks at fields and sub-sampled in lab into multiple testing bottles for water distribution and phase boundary identification; secondly, chemicals are added to the testing samples and mixed thoroughly on a shaker followed by keeping the samples in a thermostat or water bath at a desired temperature for a certain duration to allow phase separation;

Date recue/ Date received 2020-12-05 thirdly, a few small amount of samples are withdrawn using a syringe from each sample bottle at different vertical levels for subsequent water or BS&W
analysis;
finally, the water or BS&W analysis can be done using one or in combination of the three methods: centrifuge [such as ASTM D1796-11(2016), ASTM D4007-11(2016), ASTM D2709-16], distillation (such as ASTM D95 and ASTM D4006) and Karl Fischer titration [such as ASTM D4928-12(2018), ASTM D6304-16, ASTM D4017, ASTM D6869-17, ASTM E203-16, ASTM E1064-16].

[0004] Both centrifuge method and distillation method involve use of one of toxic and flammable diluents: such as toluene, xylene, petroleum naphtha, petroleum spirit and other petroleum distillates having a boiling point range of 90-210 C. There is a strong health and environmental safety concern on using such toxic and flammable diluents. The Karl Fischer titration method also involves use of toxic Karl Fisher reagents, which consist of an alcohol (ethanol or diethylene glycol monoethyl ether), a base (imidazole or pyridine), sulfur dioxide (SO2) and iodine (12). All of the three methods can only provide water or BS&W content at one or a few vertical levels of testing sample in a bottle. The centrifuge method requires at least 5 ml sample, taking 3 samples from 3 vertical levels of a 150-200 ml bottle is operable, however, taking 5 samples is extremely difficult, meaning that it is very limited for water distribution and phase boundary identification. The distillation method requires a large volume of sample, e.g. 25 ml for water content less than 10% by volume, and 200 ml for water content less than 1% by volume, meaning that it is not suitable for water distribution analysis of sample in a 150-200 ml sample bottle. Only the Karl Date recue/ Date received 2020-12-05 Fisher titration method is suitable for water distribution analysis and phase boundary identification as it just requires a small amount of sample.

[0005] Surface/interfacial energies play a very important role in various industrial processes, such as mineral separation, oil sands separation, waste water treatment, pulp and paper making, surface coating, painting, etc. Surface and interfacial properties can be conventionally measured using drop methods (sessile drop method and pendant drop method) and probe methods (Du NoCiy ring method, Du NoCiy-Padday rod method and Wilhelmy plate method). Measurement principles are well described elsewhere, such as cscscientific.com, kruss-scientific.com, rheologylab.com, sinterface.com, etc.
https://www.cscscientific.com/csc-scientific-blog/surface-tension-rings-bubbles-drops-and-plates https://www.kruss-scientific.com/services/education-theory/glossary/surface-tension/
=https://www.rheologylab.com/services/interfacial-surface-tension-testing/
http://www.si nterface.com/service/fu ndam entals/m ethods/i ndex. html,

[0006] Hence, the object of present invention is to develop a highly desirable apparatus and method that measures water content continuously and provides water content profiles, surface/interfacial levels (or phase boundaries), interfacial thicknesses and surface/interfacial tensions of multiphase dispersions using the apparatus.

Date recue/ Date received 2020-12-05 Summary of the Invention [00071 A apparatus and method is provided for simultaneously measuring water content profiles, surface/interfacial levels and interfacial thicknesses of multiphase dispersions, such as the dispersions with water dispersed in produced oils, crude oils, various fuels, distillates, lubricants, paints and polymers, or the reversed dispersions with these organic components dispersed in water. Surface or interfacial tension can also be measured thereafter using the same apparatus once the surface/interfacial levels are identified. The apparatus with 1-16 channels, namely multi-channel scanning water analyzer (MCSWA) and/or multi-channel tensiometer, comprising a motorized precision vertical stage with multiple capacitive sensors, a heating system with multiple heating cells for keeping multiple sample bottles and a data acquisition system, where the capacitive sensors can be precisely controlled via a computer to dip into the samples at a preset scanning velocity and the capacitances of the sensors are continuously measured by the data acquisition system. The measured sensor capacitances are then used to derive water content profiles, surface/interfacial levels, interfacial thicknesses and surface/interfacial tensions of the respective samples for chemical screening, engineering design and production quality assurance.
Brief Description of the Drawings [00081 Fig. 1 is a schematic illustration of a 4-channel scanning water analyzer/tensiometer.

Date recue/ Date received 2020-12-05 [0009] Fig. 2 is a schematic illustration of top view of a 4-channel scanning water analyzer/tensiometer.
[0010] Fig. 3 is a sectional illustration of the heating system.
[0011] Fig. 4 is a schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer.
[0012] Fig. 5 is an alternative schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer.
[0013] Fig. 6 is an alternative schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer using a heating block with 8 heating cells.
[0014] Fig. 7 is a schematic illustration of a 4-channel data acquisition unit.
[0015] Fig. 8 is a schematic illustration of capacitive sensors: (a) parallel plate sensor, (b) single rod sensor, (c) single rod sensor with detachable sensor head.
[0016] Fig.9 is an example of scanned curves of capacitance change C(x) and its derivative C'(x) for 2 channels (a full view).
[0017] Fig.10 is an example of the scanned curves of capacitance change C(x) and its derivative C'(x) for 2 channels (a zoom-in view).
[0018] Fig.11 is an illustration of how to obtain interfacial levels, water contents and interfacial thicknesses from the scanned curves (a zoom-in view).
[0019] Fig.12 is an illustration of how to obtain interfacial levels, water contents and interfacial thicknesses from the scanned curves (a full view).

Date recue/ Date received 2020-12-05 [0020] Fig. 13 is an illustration of the surface/interfacial tension measuring process.
[0021] Fig. 14 is an illustration of the response signals representing capacitance change C(x) and its derivative C'(x) as well as inserted excessive pulling force, Fp , as a function of time.
[00221 Fig. 15 shows actual scanned curves of capacitance change C(x) and its derivative C'(x) for de-ionized water using a 8-channel tensiometer.
[00231 Fig. 16 shows actual scanned curves of capacitance change C(x) and its derivative C'(x) for OW-20 engine oil using a 8-channel tensiometer.
Detailed Description of Preferred Embodiments [00241 The present invention is described below with reference to Fig. 1, which is a schematic illustration of a 4-channel scanning water analyzer, comprising a support station having a base frame (1), a post (2) and a clamp (3), a motorized vertical linear stage integrating a motor (4), a motor controller (5) and a motor travel guide (6) and a moving unit (7), a heating system having a heating control box (8) and multiple heating cells (9a, 9b, 9c and 9d, not all shown in Fig. 1), a sensor holder manifest (10) holding multiple sensors (11a, 11 b, 11 c and 11d, not all shown in Fig.
1), a data acquisition unit (12) attached to the vertical stage's moving unit (7) so that the data acquisition unit can move with the stage's moving unit together, a front enclosure (17) that can be manual or motorized, a fixed rear enclosure (18) and multiple glass bottles (19a, 19b, 19c and 19d, not all shown in Fig. 1) and an integrated driver for controlling the vertical stage's precise move and data acquisition as well as data

- 7 -Date recue/ Date received 2020-12-05 processing. For the motorised enclosure, there are a motor (13), a motor controller (14), a cylinder (15), an extendable/retractable moving rod (16) and the enclosure (17). Each data acquisition unit (12) has 4 channels. The multi-channel can be any even number from 2-16, of course, it can also be single channel as well. Each channel requires a heating cell, a respective sensor and a glass bottle with testing sample. Multiple data acquisition units can be used for an apparatus with number of channels greater than 4 and can be directly connected to a computer via multiple USB ports or via a USB hub. The motor controllers (5) and (14) can also be connected directly to the computer either via USB ports or the USB hub. It is preferable to use a USB 2.0 or 3.0 hub to integrate all controllers into one connection point to the computer. It would be a good option to use a low voltage (5 - 12 V) motor (13) for the front enclosure (17) so that the enclosure can be operated by either a power supply or a battery set. The use of a battery set can avoid a hanging power cable for the motor (13) that move the enclosure up and down. The fixed rear enclosure (18) is detachable for easy electrical maintenance. The heating control box has a temperature controller, a fuse, a power switch, a solid state relay, a power distribution unit connecting to multiple cartridge heaters.
[00251 Referring to Figs. 2, which is a schematic illustration of top view of a 4-channel scanning water analyzer/tensiometer, having 4 heating cells (9a, 9b, 9c and 9d) arranged center-symmetrically. The sensor holder manifest (10) has 2 round bars or tubes (20a and 20b) working as guides for positioning the 4 sensors precisely.
The 4 sensors are hung on the guides via 4 pieces of 90 adapters (21a, 21b, 21c and 21d). The electrical wires connecting each sensor are shielded and enclosed in a

- 8 -Date recue/ Date received 2020-12-05 wire channel metal box (22) to its data acquisition unit (12). The electrical wires connecting each sensor can also be tied to and routed along the sensor holder (10) directly to the data acquisition unit (12). To minimize noises the data acquisition unit (12), the sensor holder manifest (10) with sensors (11 a, lib, 11 c and 11d) and the electrical wire channel metal box (22) are all attached to the motor's moving unit (7) and move together in a whole.
[00261 Referring to Fig. 3, which is a sectional illustration of the heating system having a heating control box (8) and multiple heating cells (9a, 9b, 9c and 9d, not all shown in Fig. 3). Each heating cell has 3 cartridge heaters (23) inserted in its wall of the metal ring (24) surrounded by insulation materials (25 around and 26 bottom), the insulated heating cell is then sitting on a base plate (27) made of also one of the insulation materials, which can be fiberglass, mica, mineral fibber, refractory cement, etc., preferably mineral fibber and mica.
[00271 Referring to Fig. 4, which is a schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer, having 8 heating cells that are grouped into 2 sets, one set (9a, 9b, 9c, and 9d) is on the left side and another set (9e, 9f, 9g and 9h) is on the right side of the centered cylinder (15). The sensor holder manifest (10) has 4 round bars or tubes, two (20a and 20b) working as guides for positioning precisely the 4 sensors on the left side and other two (20c and 20d) working as guides for positioning precisely the 4 sensors on the right side. The electrical wires connecting all sensors on the left side are shielded and enclosed in a wire channel metal box (22a) to its data acquisition unit (12a, not shown in Fig 4) and all sensors on the right side are shielded and enclosed in a wire channel metal box (22b) to its

- 9 -Date recue/ Date received 2020-12-05 data acquisition unit (12b, not shown in Fig.4). The electrical wires connecting each sensor can also be tied to and routed along the sensor holder manifest (10) directly to the data acquisition unit (12).
[0028] Referring to Fig. 5, which is an alternative schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer, having 8 heating cells that are grouped into 2 sets, one set (9a, 9b, 9c, and 9d) is on the top side and another set (9e, 9f, 9g and 9h) is on the bottom side of the centered cylinder (15). The sensor holder manifest (10) has 2 round bars or tubes (20a and 20b) working as guides for positioning precisely the 8 sensors. The electrical wires connecting each sensor are tied to and routed along the sensor holder manifest (10) directly to the data acquisition unit (12).
[0029] Referring to Fig. 6, which is an alternative schematic illustration of top view of a 8-channel scanning water analyzer/tensiometer, having 8 heating cells (9a, 9b, 9c, 9d, 9e, 9f, 9g and 9h) and 15 cartridge heaters (23) in a heating block (24), which is surrounded by insulation materials (25). The sensor holder manifest (10) has 2 round bars or tubes (20a and 20b) working as guides for positioning precisely the 8 sensors. The electrical wires connecting each sensor are tied to and routed along the sensor holder manifest (10) directly to the data acquisition unit (12).
[0030] Referring to Fig. 7, which is a schematic illustration of a 4-channel data acquisition unit (12). It comprises 4 LC-tanks for connecting 4 capacitive sensors, a high precision frequency counter with a multiplexer or a data selector and a USB
microcontroller. Each LC tank has an inductor (L) and two capacitors (Ca and Cs)

- 10 -Date recue/ Date received 2020-12-05 connected in parallel to form a resonance circuit. Its resonance frequency (F) can be expressed as [0031] F= 1 , _____________________________________________________ (1), 211-11L(Ca+C,) [0032] where L is inductance of the inductor, Ca is the capacitance of an adjustable capacitor and C, is the capacitance of a variable capacitor, which is actually the sensor's capacitance. The resonance frequency is measured using a high precision analog to digital frequency converter or counter having at lease 21-bit resolution, preferably greater than 24-bit resolution and equal or less than 32-bit resolution. The measured frequency is then read by the USB microcontroller unit via different communication interfaces, e.g. I20, UART, LVDS, SPORT, SPI or PPI, preferably the I20 protocol, which is an inter-integrated circuit. It uses only two lines for communication, a serial data line (SDA) for master and slave to send and receive data, and a serial clock line (SCL) for carrying clock signal. The adjustable capacitors are used to bring all channel's capacitance as close to each other as possible, and it is beneficial to use 4 inductors with inductance value as close to each other as possible, so that the measured frequencies are as close as possible in the beginning of a baseline period. The operating frequency range can be adjusted by using different inductors with different inductance values; the preferable operating frequency range is 800 - 6000 kHz, in which surrounding noises can be minimized.
The high resolution frequency counter has a multiplexer or a data selector, which can be programmed in sequence to measure the frequency of a channel at a time to

- 11 -Date recue/ Date received 2020-12-05 avoid cross-talking between channels. Each data acquisition unit can support a channel apparatus, and 2 data acquisition units are required to support a 8-channel apparatus. To increase signal stability the inductors and capacitors as well as connecting wires are all shielded and share the same electrical ground (GND) as the frequency counter and the microcontroller. Capacitance of a sensor can be calculated using , 0, 1 'y [0033] C, = ¨ Ca ______________________________ (2), L12.7-cF1 [0034] and its derivative as a function of bottle mark (x or sample volume) is [0035] C'(x)¨ dC '(x) ¨ dC(x) (3), dx dx [0036] where total capacitance C(x)= C,(x)+ Ca (4).
[0037] Referring to Fig. 8, which is a schematic illustration of capacitive sensors: (a) parallel plate sensor, (b) single rod sensor and (c) single rod sensor with detachable sensor head. The parallel plate sensor (Fig.8a) comprises two stainless steel plates, one as a positive electrode (29a), another one as a negative electrode (29b).
The two plates are spaced with a rectangle column electrical insulation material (30) and center positioned in a stainless steel round tube (31) and firmly attached to its wall using non-conductive epoxy glue (32). The stainless steel round tube also works as a shielding tube and is connected at a point (33) to the shielding conductor (34) of an audio 3-conductor receptacle (35). The positive electrode (29a) and the negative electrode (29b) are connected to other two conductors (36 and 37) respectively. A

- 12 -Date recue/ Date received 2020-12-05 stereo audio cable (38) is used to connect the sensor to a channel's connector on the data acquisition unit (12).
[0038] The single rod capacitive sensor (Fig. 8b) is similar to the parallel plate sensor (Fig.8a) in connecting itself to the audio 3-conductor receptacle (35). The difference is that the positive electrode (29a) is replace with a stainless steel rod (39), and the negative electrode (29b) is shrunk to a small metal ring (40), which can be copper or stainless steel. The rectangle column electrical insulation material (30) is replaced with a thin film insulation material (41). The parallel plate sensor can provide higher measurement accuracy than the single rod sensor, but the former is a bit inconvenient in cleaning after each test.
[0039] The single rod capacitive sensor (Fig. 8c) is also similar to the single rod capacitive sensor (Fig. 8b) in connecting itself to the audio 3-conductor receptacle (35). The difference is that the positive electrode (39) is split into two parts, the detachable sensor head (39a) and the fixed sensor adapter (39b); the detachable sensor head (39a) is screwed on the fixed sensor body (39b) and can be unscrewed for easy cleaning operation; while the fixed sensor adapter (39b) is permanently attached to the sensor body.
[0040] Referring to Fig. 9, which is an example of scanned curves of capacitance C(x) and its derivative C'(x) for 2 channels (for sample bottles A and B), where Ca (x) and Cb(x) are capacitance changes relative to a baseline reference, Ca '(x) and Cb'(x) are derivatives of the capacitance changes for corresponding sample bottles A and B, and x is bottle mark in ml. The equally spaced bottle marks normally

- 13 -Date recue/ Date received 2020-12-05 represent respective volumes in the middle part, but slightly different from respective volumes at top and bottom parts of a bottle. The derivative, C '(x)¨ dC(x) is derived dx ' from C(x) using a moving multiple points polynomial curve fitting. There are 4 phases in bottle A, their interfaces are labelled as Al, A2, A3 and A4 in the inserted photo, where the 4 phases are a clean oil phase between Al and A2, an emulsion phase between A2 and A3, a rag layer phase between A3 and A4 and an aqueous phase at the bottom. There are only 2 phases in bottle B, their interfaces are labelled as B1 and B2, where the 2 phases are a clean oil phase at the top and an emulsion phase at the bottom.
[00411 Referring to Fig. 10, which is a zoom-in view of the scanned curves of capacitance C(x) and its derivative C'(x) for 2 channels (for sample bottles A
and B), all labels share the same meaning as in Fig. 9 for the inserted photo.
[0042] Referring to Figs 11 and 12, which are illustrations of how to obtain interfacial levels and water contents from the scanned curves. The derivative C'(x) is advantageous in interfacial level identification as it shows spikes at every interface, denoted using volume in ml starting from bottom of a bottle, e.g. Al (160.00 ml), A2 (107.90 ml), A3(48.03 ml) and A4 (28.18 ml) for sample bottle A; B1 (154.70 ml) and B2 (75.89 ml) for sample bottle B. The coordination values [x, C'(x)] are shown simultaneously on the computer screen when the vertical cursor lines are dragged and moved. The water contents in different phases can be obtained from capacitance C(x) curve using linear fitting for specified data ranges that show linear

- 14 -Date recue/ Date received 2020-12-05 trends. Water content by volume percent, W(x), is proportional to the slope, S(x) , of a linear-fitted line, [0043] W(x)=KS(x) (5), [0044] where K is a capacitive coefficient of a testing sample. So, one can have Wa(x)= KaSa(x) , Wb(x)= KbSb(x) , etc. where Ka and Kb are the capacitive coefficients of samples A and B respectively, which can be obtained using a calibration curve.
[0045] Water content, W(x), is a constant for a linear period of curve C(x), such as all data between bottle mark range (Xa1, Xa2) can be used to derive water content in the top clean oil phase, (Xa3, Xa4) for water content in the emulsion phase, (Xa5, Xa6) for water content in the rag layer and (Xa7, Xa8) for water content in aqueous phase in bottle A; similarly, bottle mark range (Xb1, Xb2) for water content in the top clean oil phase and (Xb3, Xb4) for water content in the emulsion phase in bottle B. A
summary of processed data is shown below.
Sample Phase name Interfacial level Bottle mark range Slope, S(x) ID ml Label ml ml fF/m1 Clean oil phase Al: 160.00 Xal ,Xa2 154/ 109.8 6.99 A Emulsion phase A2: 107.90 Xa3, Xa4 100/ 82.3 9i7 Rag layer phase A3: 48.03 Xa5,Xa6 44.9 38.3 182.20 Aqueous phase A4: 28.18 Xa7,Xa8 24.4 18.0 193.10 Clean oil phase Bl: 154/0 Xbl, Xb2 148.4 109.8 T50 Emulsion phase B2: 75.89 Xb3,Xb4 4T4 35.4 93.21 [0046] It is noted that for chemical ranking, slope, S(x), derived from capacitance value can be directly used without converting it to water content using a calibration

- 15 -Date recue/ Date received 2020-12-05 curve, because they correlate monotonically and share the same trend. The higher slope value the higher water content in the corresponding phase, such as (1) water content in the clean oil phase is higher in bottle B than in bottle A due to that slope value is higher for the respective phase in bottle B (7.50 fF/m1) than in bottle A (6.99 fF/m1); (2) water content in the emulsion phase is significantly higher in bottle B than in bottle A due to that slope value is higher for the respective phase in bottle B (93.21 fF/m1) than in bottle A (9.17 fF/m1); and (3) water content increases from the clean oil phase through the aqueous phase in bottle A due to that slope values are in an ascending order: 6.99, 9.17, 182.20 and 193.10 fF/ml. This is a very unique feature of present invention in chemical screening tests.
[0047] It is also noted that derivative C'(x) has the same meaning as slope value S(x) if the bottle mark x range is narrow enough for linear fitting.
Hence, C'(x) curves can be directly used for chemical ranking in a chemical screening test, excluding those spikes for phase boundary identification.
[0048] A spike of the derivative C'(x) represents additional capacitance of the respective interface, which is a measure of excess charges, Q, at the interface and can be evaluated using the area of the spike or be calculated directly using capacitance change over the spike, [0049] Q=C(x2)¨C(xl) (6), [0050] where xl and x2 are the onset and offset of the spike. In other words, interfacial thickness, ö, can also be evaluated by

- 16 -Date recue/ Date received 2020-12-05 [0051] 8 = x2¨xl (7)-[0052] Interfacial thickness can be used as an additional marker for evaluating chemical performance, the greater the interfacial thickness the harder for oil/water phase separation.
[0053] Both surface and interfacial tensions can be measured with acceptable accuracy for chemical ranking or chemical selection using the multi-channel scanning water analyzer (MCSWA) directly, which make it a multi-channel tensiometer.
The working principle is similar to and a variation of the Du No0y-Padday rod method. It uses multiple stainless steel rods with a cone-shaped tip as capacitive sensors in conjunction with the MCSWA's fully automated positioning system that can precisely achieve 0.06 % accuracy and 0.04 jam resolution. Fig. 13 is an illustration of the surface/interfacial tension measuring process for a single sensor. Multiple sensors are arranged in parallel and automatically controlled for a multi-channel tensiometer, which is a bonus function of the multi-channel scanning water analyzer.
[0054] In a measurement scan, the sensors move down from one medium (e.g. the air for surface tension or a liquid for interfacial tension) and dip into another liquid medium and hold in the liquid medium for a short time duration and then rise up to its original position.
[0055] During the sensor rising period, the excessive force that needs to pull the sensor up is equal to the weight of the meniscus pulled up above the reference level.
The reference level is the flat meniscus before the sensor's contact with the liquid. If

- 17 -Date recue/ Date received 2020-12-05 the sensor tip is at a distance Ah above the reference level then the excessive vertical pulling force, Fp, can be expressed as [0056] F p= 71- d / cos a +V ni(P 2 ¨ Pi)g (8) [0057] where 7 denotes the interfacial tension between the liquid and the surrounding medium, zd denotes the wetted perimeter and d the wetted diameter, and a is the angle between the liquid and the gravity direction, which can be calculated using [0058] a = u (9) [0059] where 0 is the contact angle between the liquid and the sensor's cone surface, is the cone shape angle. The second part of equation (8) represents the net gravitational force excluding the buoyancy, where Vni is the volume of the meniscus pulled up above the reference level, pi and p2 are the densities of the two media, g the gravitational acceleration constant.
[0060] Considering the cone-shaped sensor tip that makes the meniscus as an elastic thin liquid string during pulling, the gravitational part is a few order of magnitude below the first surface tension part, hence equation (8) can be rewritten as, [0061] Fp = 7-Cd 7COS a. (10)

- 18 -Date recue/ Date received 2020-12-05 [0062] For the sensor rising period, the excessive pulling force on the sensor is approximately proportional to the height of the meniscus as the blue curve shown in Fig. 14, which is an illustration of the response signals representing capacitance change, C(t), and its derivative, CV), as well as inserted excessive pulling force, Fp, as a function of time.
[0063] Fp= k Ah , (11) [0064] where k is a sensor constant.
[0065] Combining equations (10) and (11), the excessive pulling force on the sensor at the detaching point, Fdet aclung can be given as below, Lim Lim Fdet aching = FP = z d 7 cos a = zd. 7= k Ahmax , (12) d [0066] where d11 is the minimum diameter of the liquid medium relating to the sensor, which is a characteristic of the sensor, depending on the surface roughness and the angle sharpness of the cone-shipped sensor tip. Akax is the maximum height of the meniscus at the minimum wetting diameter, c 1 . The meniscus liquid string will break if the sensor is further pulled up. Rearranging equation (12) the surface tension 7 can be obtained, [0067] = k (13) 7C cl.õõ Ahmax

- 19 -Date recue/ Date received 2020-12-05 [0068] Ahmax can be derived via numerical data processing using recorded capacitance change, C(t), and its derivative function, CV). The coefficient, 71-d.
can be obtained using a reference liquid with known surface tension, such as water for aqueous systems, xylene for hydrocarbons.
[0069] The capacitance change, C(t) , of the sensor shows a sharp increase/decrease at the attaching and detaching points, which are identified by a maximum and a minimum points ( tmax and tn. ) of its derivative function, C
V), as illustrated in Fig. 14. Each sensor tip's vertical position at the attaching point, p(tmax) , and the detaching point, P(t1) , can be obtained numerically via a linear interpolation using recorded tip position function, p(t), Ahmax can then be found by [0070] Ahrna. = P(tõ)¨P(caõ). (14) [0071] Figs. 15 and 16 show the actual scanned curves of capacitance changes, C(t), and its derivative function, C'(t), for de-ionized water and OW-20 engine oil respectively using a 8-channel tensiometer. Eight surface tension values of 8 samples can be obtained in one test run.
[0072] The multi-channel scanning water analyzer or tensiometer is a very compact design making it portable for both lab and field tests. Number of channels can be selectable from 1 up to 16, preferably even numbers. Its multi-function (water content profile analysis, surface and interfacial level identification and tension measurement) make it a cost effective instrument for different applications.
The

-20 -Date recue/ Date received 2020-12-05 multi-channel scanning measurement makes chemical selection efficiently and environmental friendly. Critical micelle concentration of a surface active agent can be measured in one test run.
[0073] The present invention meets the trend of energy digitization.

- 21 -Date recue/ Date received 2020-12-05

Claims

Claims:
[0074] Embodiments of the present invention are described as follows:

1. A multi-channel scanning apparatus for measuring water content profiles, surface/interfacial levels, interfacial thicknesses, surface/interfacial tensions of multiphase dispersions, such as dispersions with water dispersed in produced oils, crude oils, various fuels, distillates, lubricants, paints and polymers or reversed dispersions with these organic components dispersed in water.

2. The apparatus of claim 1, wherein the multi-channel can be 1 through 16 selectable, preferably even numbers 2 through 16.

3. The apparatus of claim 1, wherein the apparatus comprises a support station having a base frame, a post and a clamp, a motorized vertical linear stage integrating a motor, a motor controller and a motor travel guide and a moving unit, a heating system having a heating control box and multiple heating cells, a sensor holder manifest holding multiple sensors, a data acquisition unit attached to the vertical stage's moving unit so that the data acquisition unit can move with the stage's moving unit together, a front enclosure that can be manual or motorized, a fixed rear enclosure and multiple glass bottles and an integrated driver for controlling the vertical stage's precise move and data acquisition as well as data processing. For the motorised enclosure, there are a motor, a motor controller, a cylinder, an extendable/retractable moving rod and the enclosure. Each data acquisition unit has 4 channels. The multi-channel can be any even number from 2 through 16; of course, it can also be Date Recue/Date received 2020-12-05 single channel as well. Each channel requires a heating cell, a respective sensor and a glass bottle with testing sample. Multiple data acquisition units can be used for an apparatus with number of channels greater than 4 and can be directly connected to a computer via multiple USB ports or via a USB hub.
The motor controllers can also be connected directly to the computer either via USB ports or the USB hub. It is preferable to use a USB 2.0 or 3.0 hub to integrate all controllers into one connection point to the computer. It would be a good option to use a low voltage (5 - 12 V) motor for the front enclosure so that the enclosure can be operated by either a power supply or a battery set.
The use of a battery set can avoid a hanging power cable for the motor that move the enclosure up and down. The fixed rear enclosure is detachable for easy electrical maintenance. The heating control box has a temperature controller, a fuse, a power switch, a solid state relay, a power distribution unit connecting to multiple cartridge heaters.

4. The apparatus of claims 1 and 3, wherein the heating cells are arranged center-symmetrically, the sensor holder manifest has 2 round bars or 4 round bars working as guides for positioning sensors precisely depending on the configuration of the heating cells as shown in Figs 4 and 5. The sensors are hung on the guides via 90 adapters. The electrical wires connecting each sensor are shielded and enclosed in a wire channel metal box to its data acquisition unit. The electrical wires connecting each sensor can also be tied to and routed along the sensor holder directly to the data acquisition unit.
To minimize noises the data acquisition unit, the sensor holder manifest with Date Recue/Date received 2020-12-05 sensors and the electrical wire channel metal box are all attached to the motor's moving unit and move together in a whole.

5. The apparatus of claims 1 and 3, wherein the heating system, as shown in Fig. 3, has a heating control box and multiple heating cells. Each heating cell has 3 cartridge heaters inserted in its wall of the metal ring surrounded by insulation materials, the insulated heating cell is then sitting on a base frame made of also one of the insulation materials, which can be fiberglass, mica, mineral fibber, refractory cement, etc., preferably mineral fibber and mica.

6. The apparatus of claims 1, 3 and 4, wherein the heating cells are grouped into 2 sets, one set is on the top side and another set is on the bottom side of the centered cylinder. The sensor holder manifest has 2 round bars or tubes working as guides for positioning precisely the sensors. The electrical wires connecting each sensor are tied to and routed along the sensor holder manifest directly to the data acquisition unit.

7. The apparatus of claims 1, 3 and 6, wherein the heating cells and cartridge heaters are integrated in a heating block, which is surrounded by insulation materials as shown in Fig. 6. The sensor holder manifest has 2 round bars or tubes working as guides for positioning precisely the sensors. The electrical wires connecting each sensor are tied to and routed along the sensor holder manifest directly to the data acquisition unit.

8. The apparatus of claims 1 and 3, wherein the data acquisition unit comprises 4 LC-tanks for connecting 4 capacitive sensors, a high precision frequency Date Recue/Date received 2020-12-05 counter with a multiplexer or a data selector and a USB microcontroller. Each LC tank has an inductor (L) and two capacitors (Ca and Ca) connected in parallel to form a resonance circuit. The resonance frequency is measured using a high precision analog to digital frequency converter or counter having at lease 21-bit resolution, preferably greater than 24-bit resolution and equal or less than 32-bit resolution. The measured frequency is then read by the USB microcontroller unit via different communication interfaces, e.g. I2C, UART, LVDS, SPORT, SPI or PPI, preferably the I2C protocol, which is an inter-integrated circuit. It uses only two lines for communication, a serial data line (SDA) for master and slave to send and receive data, and a serial clock line (SCL) for carrying clock signal. The adjustable capacitors (Ca) are used to bring all channel's capacitance as close to each other as possible. The operating frequency range can be adjusted by using different inductors with different inductance values; the preferable operating frequency range is 800 -6000 kHz, in which surrounding noises can be minimized. The high resolution frequency counter has a multiplexer or a data selector, which can be programmed in sequence to measure the frequency of a channel at a time to avoid cross-talking between channels. Each data acquisition unit can support a 4-channel apparatus, and 2 data acquisition units are required to support a 8-channel apparatus, and 3 data acquisition units are required to support a 12-channel apparatus, and 4 data acquisition units are required to support a 16-channel apparatus. To increase signal stability the inductors and Date Recue/Date received 2020-12-05 capacitors as well as connecting wires are all shielded and share the same electrical ground (GND) as the frequency counter and the microcontroller.

9. The apparatus of claims 1, 3 and 8, wherein the capacitive sensors can be (a) parallel plate sensor, (b) single rod sensor and (c) single rod sensor with detachable sensor head. The parallel plate sensor comprises two stainless steel plates, one as a positive electrode, another one as a negative electrode.
The two plates are spaced with a rectangle column electrical insulation material and center positioned in a stainless steel round tube and firmly attached to its wall using non-conductive epoxy glue. The stainless steel round tube also works as a shielding tube and is connected at a point to the shielding conductor of an audio 3-conductor receptacle. The positive electrode and the negative electrode are connected to other two conductors respectively. A stereo audio cable is used to connect the sensor to a channel's connector on the data acquisition unit.

10. The apparatus of claims 1, 3 and 9, wherein the single rod capacitive sensor (b) is similar to the parallel plate sensor (a) in connecting itself to the audio 3-conductor receptacle. The difference is that the positive electrode is replace with a stainless steel rod having a cone-shaped sensor tip, and the negative electrode is shrunk to a small metal ring, which can be copper or stainless steel. The rectangle column electrical insulation material is replaced with a thin film insulation material. The parallel plate sensor can provide a higher measurement accuracy than the single rod sensor, but the former is a bit inconvenient in cleaning after each test.

Date Recue/Date received 2020-12-05

11.The apparatus of claims 1, 3, 9 and 10, wherein the single rod capacitive sensor (c) is also similar to the single rod capacitive sensor (b) in connecting itself to the audio 3-conductor receptacle. The difference is that the positive electrode is split into two parts: a fixed sensor head adapter permanently attaches to the sensor and a detachable sensor head having a cone-shaped tip; the detachable sensor head is screwed on the fixed sensor head adapter and can be unscrewed for easy cleaning operation.

12. The apparatus of claim 1, wherein the water content profiles, surface/interfacial levels and interfacial thicknesses of multiphase dispersions are measured simultaneously by dipping the sensors into respective testing samples at a preset scanning velocity of 0.1-0.2 mm/s, the scanned curves of capacitance change C(x) and its derivative C'(x) are used to derive water content profiles, surface/interfacial levels and interfacial thicknesses of the multiphase dispersions. The derivative, C '(x)¨ dC(x) , is derived from C(x) dx using a moving multiple points polynomial curve fitting. The derivative C'(x) is advantageous in interfacial level identification as it shows spikes at every interface. The water contents in different phases can be obtained from capacitance change C(x) curve using linear fitting for specified data ranges that show linear trends.

13.The apparatus of claim 1, wherein the surface/interfacial tensions of multiphase dispersions are measured by dipping the sensors into respective test samples at a preset scanning velocity of 0.02-0.20 mm/s then rising the Date Recue/Date received 2020-12-05 sensors till the attached meniscuses break, the scanned curves of capacitance change C(x) and its derivative C'(x) are used to derive surface/interfacial tensions. The derivative function, C V) , shows a sharp increase/decrease at the attaching and detaching points, which are identified by a maximum and a minimum points (t maõ and tinin) of its derivative function as illustrated in Fig. 14. Each sensor tip's vertical position at the attaching point, p(t.a.) , and the detaching point, P(t min) , can be obtained numerically via a linear interpolation using recorded tip position function, p(t), Ahma.
can then be found by Aka. = P(t. )¨P(tina.) and the surface tension 7 can be obtained by 7 ¨ ___________ Ah where The coefficient, __________________ , can be obtained 7/- d min max c 1 ina.
using a reference liquid with known surface tension, such as water for aqueous systems, xylene for hydrocarbons.

Date Recue/Date received 2020-12-05